Earth pigments in painting: characterisation and differentiation by means of FTIR spectroscopy and SEM-EDS microanalysis

Analytical characterisation of natural earths (ochres, siennas, umbers and green earths) has been carried out using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) coupled to an energy dispersive X-Ray spectrometer (EDS). The study of these pigments, which are found in works of art, is very important since it can shed light on their source or the pictorial technique used. FTIR spectroscopy is suitable for the identification and differentiation of ochres and siennas. According to the matrix of the sample, FTIR allows the classification of ochres into ochres containing kaolinite and ochres containing sulphate. One of the goals of this research has been to establish a relationship between the matrix and the source of the samples tested. SEM-EDS is probably a better technique than FTIR for characterising umbers and green earths since they do not exhibit significant differences when FTIR studies are performed.     

Ochre-differentiation through micro-Raman and micro-FTIR spectroscopies: application on wall paintings at Meteora and Mount Athos, Greece

The most widely-used inorganic pigments of Byzantine and post-Byzantine hagiography are earth pigments called ochres such as, red and yellow ochres, limonite, goethite, raw and burnt sienna, caput mortuum and hematite. The present experimental work proposes a technique of differentiation that allows one to distinguish among all the different kinds of iron oxides, thereby providing a better understanding of the painting technique used on portable icons and wall paintings. The ratios between the main spectroscopic peaks, attributable to the major components usually present in ochres, were calculated and compared, one against the another, from the spectra obtained through micro-Raman spectroscopy. Elementary composition is also revealed through a scanning electron microscopy (SEM) analysis. The possibility for detailed study on a particular Byzantine ochre palette can thus be performed based on the small differences in its nature and composition. These differences can first be observed and then measured among all of the natural earth pigments, through microRaman and microFTIR spectroscopies.     

Study of mural paintings using in situ XRF, confocal synchrotron-μ-XRF, μ-XRD, optical microscopy, and SEM-EDS--the case of the frescoes from Misericordia Church of Odemira

In this work, we present the results of an analytical method developed for detailed pigment identification, stratigraphy, and degradation of the paint layers of mural paintings applied in the study of the 17th century frescoes from the Misericordia Church of Odemira (Southwest Portugal). In situ X-ray fluorescence spectrometry analyses were performed on three panels of the mural paintings and complemented by colorimetric measurements. The different color areas were also sampled as microfragments (approx. 1 mm2) that were studied as taken or mounted in epoxy resin to expose the different paint layers. The microfragments of paint layers and their cross sections were characterized by optical microscopy and scanning electron microscopy coupled with energy dispersive X-ray spectrometry. Furthermore, elemental analysis was obtained with spatially resolved confocal synchrotron radiation μ-X-ray fluorescence spectrometry performed at ANKA synchrotron FLUO beamline. Occasionally, phase analysis by μ-X-ray diffraction was also performed. Results from the different techniques allowed pigment identification and, in some cases, the evaluation of color changes due to degradation processes and, considering the Southern Portugal geology, the identification of their possible provenance. The pigments used were essentially yellow, brown and red ochres, smalt blue, copper green, and black earths, probably from local sources.     

Voltammetric analysis of iron oxide pigments

Eighteen earthy and four pure synthetic pigments containing alpha-Fe2O3 (hematite), alpha-FeOOH (goethite) and poorly crystalline Fe and Mn oxide species were analyzed by voltammetry of microparticles. Three natural samples were subjected to an interlaboratory test to evaluate the reproducibility of the voltammetric peak potentials and peak shapes. The results confirmed that linear-sweep voltammetry is able to distinguish between poorly crystalline, ferrihydrite-like oxides and well-crystalline hematite and goethite and to detect XRD-amorphous Mn(III,IV) oxides via the peak occurrence. Voltammetry is further able to distinguish between pigments containing well-crystalline goethite (according to its structural features) and hematite (according to its particle size). The microsamples of primers from two baroque paintings were also analyzed by XRD and voltammetry and shown to be analogous to common clayey ochres.     

Byzantine wall paintings from Kastoria, northern Greece: spectroscopic study of pigments and efflorescing salts

This study concerns the investigation of pigments and efflorescence phenomena on the wall paintings of Kastoria, a rural, non-metropolitan Byzantine town. A large number of representative samples were collected from the murals of three churches, dated to post-Byzantine era (14th-17th c. AD). The identified pigments for the red colour were hematite (Fe2O3), cinnabar (HgS) and minium (Pb3O4), while brown and yellow colours were attributed to mixtures of ochres (Fe-oxides and hydroxides) and lime. The utilization of admixtures of iron, lead and mercury compounds was also attested in order to render specific tones on the painted surfaces. Black and dark blue hues were prepared using black carbon and Mn in some cases. Grey colours were assigned to a mixture of black carbon and lime. Green colour is rather attributed to admixtures of Fe-rich minerals and lime and not to the commonly used green earths. Baryte (BaSO4) was also evidenced as a filler or extender. Phosphorous was detected and connected to proteinaceous material and Mo and Sb were traced which are probably affiliated to Fe-oxides. Regarding efflorescing salts, the determined compounds are: calcite, dolomite, gypsum, halite, nitratine, natron and mirabilite, all of which are related to temperature and humidity changes and moisture fluctuations inside the wall paintings.     

Raman,X‐Ray Fluorescence Spectroscopies and Graphene Oxide Modified Screen Printed Electrodes to Identify the Pigments and Earth Present in Ancient Leather Samples

Micro‐Raman and X‐Ray Fluorescence combined with electrochemical techniques proved to be suitable for the unambiguous identification of the green pigment in a very deteriorated historical leather. The colouring matter resulted in a mixture of blue and yellow. Raman identified the blue indigo, whereas iron and arsenic were identified by XRF. The redox status of these two elements was investigated by Square Wave Cathodic Stripping Voltammetry (SWCSV). Results demonstrated the presence of As(III), probably As₂S₃ (orpiment), and Fe(III), characterising the red earths. The quantitative results obtained by SWCSV were also confirmed for Fe and As by ICP‐MS (Inductively Coupled Plasma Mass spectrometry). Voltammetric techniques, applied here for the identification of the redox status of the elements, contained in pigments, are useful to understand two important aspects: the chemical‐physical composition of the colors and the best strategy to be applied for the preservation of the pigments in ancient/deteriorated artwork objects.     

Electrochemical analysis of the alterations in copper pigments using charge transfer coefficient/peak potential diagrams. Application to microsamples of baroque wall paintings attached to polymer film electrodes

The alteration of copper pigments in art samples was studied by linear scan and cyclic voltammetry using sample-modified Elvacite 2044 film electrodes on the basis of two-dimensional diagrams of charge transfer coefficients calculated from Tafel plots of reductive dissolution processes vs. peak potential. Characteristic voltammetric peaks were obtained for pigments used in the baroque vault frescoes of the Basílica de la Virgen de los Desamparados painted by Antonio Palomino. Results obtained by voltammetric techniques were compared with those from SEM/EDX and FT-IR analysis obtaining a good agreement and leaving to an unambiguous identification of pigments used by Palomino and their alteration products.     

Electrochemical analysis of the alterations in copper pigments using charge transfer coefficient/peak potential diagrams. Application to microsamples of baroque wall paintings attached to polymer film electrodes

The alteration of copper pigments in art samples was studied by linear scan and cyclic voltammetry using sample-modified Elvacite 2044 film electrodes on the basis of two-dimensional diagrams of charge transfer coefficients calculated from Tafel plots of reductive dissolution processes vs. peak potential. Characteristic voltammetric peaks were obtained for pigments used in the baroque vault frescoes of the Basílica de la Virgen de los Desamparados painted by Antonio Palomino. Results obtained by voltammetric techniques were compared with those from SEM/EDX and FT-IR analysis obtaining a good agreement and leaving to an unambiguous identification of pigments used by Palomino and their alteration products.     

Utilisation of industrial waste for ferrite pigments production

Preliminary results of research focused on the utilisation of specific waste from metallurgical and mining activities to obtain ferrite pigments are presented. As a source of iron in the spinel-type ferrites with the general structure MFe₂O₄ (where M is a bivalent metal such as Ca and Zn), three types of industrial wastes were used: metallurgical slag from the production of non-ferrous metals and two types of AMD (acid mine drainage) sludge: one of natural origin (Fe-sediment) and the second one synthetically prepared from AMD (Fe-precipitate). This waste was homogenised by ZnO and CaCO₃ in various stoichiometric ratios n(Ca): n(Zn): n(Fe) and calcined at the temperature of 1000–1095°C. Mineralogical (XRD) analysis of the metallurgical slag pigments confirmed the formation of zinc ferrite and hematite only (Ca from reaction components entered into other phases). The ferric component of the AMD sludge (Fe-precipitate and Fe-sediment) formed a mixture of zinc ferrite, calcium ferrite, and hematite while increased calcination temperature supported the ferritic structure formation. Prepared pigments have no considerable colour differences; they were in brown colour tones. Pigments from the AMD sludge were more dark brown coloured than those from slag. Pigments were applied in an alkyd-resin paint and consequently basic anticorrosive tests were performed. Pigments obtained from metallurgical slag showed better anticorrosive properties than those from AMD. However, because of high Pb content in pigments from the slag (0.67–1.10 mass % Pb in pigments), utilisation of these pigments in coatings is problematic. Ferrite pigments from the AMD sludge, mainly that with zinc ferrite, have promising application in anticorrosive paints but optimisation of the preparation process is required.     

Analysis of earthy pigments in grounds of Baroque paintings

Sixteen samples of orange-red and yellow Fe-oxide earthy pigments mainly from bole grounds of Baroque paintings were studied by elemental and phase analysis and voltammetry. Fe, K, and Ti content were found to be suitable for further classification of those earthy pigments. According to the chemical and phase composition the yellow grounds were natural yellow ochres formed by intense chemical weathering in a moderate climate. Very similar phase and elemental composition of part of the orange-red boles indicated their similar geological origin or even their formation by calcination of yellow ochres. Part of the orange-red boles differed significantly from the yellow boles, especially in their increased content of Ti, indicating their relation to end products of intense weathering, e.g. laterites formed in a tropical climate. Analogous materials with a correspondingly large Ti content are not currently commercially available and their geological origin (provenance) is not clear. In several orange-red boles the intentional addition of rather coarse-grained haematite to natural ochre by the painters was assumed on the basis of Fe oxide content and crystallinity.     

Characterization of Wallpaintings from the Caliphal Baths of Cordoba (Spain) by X-Ray Diffraction and Raman Microspectroscopy

Wallpainting fragments from the Caliphal Baths of Cordoba, Spain, were studied in this work for the first time. X-ray diffraction (XRD) and Raman microspectroscopy allowed the chemical nature of the pigments used by the Arabic artists of the time to be identified. All pigments were applied over a gypsum priming layer. The white, red, and yellow colors used were obtained from gypsum, hematite, and goethite, respectively. Some pigments were prepared by mixing these materials. The analytical techniques used also allowed the mortar material to be identified. The results of this study may be useful to develop effective conservation strategies for archaeological remains.     

A Titanium‐Doped SiOx Passivation Layer for Greatly Enhanced Performance of a Hematite‐Based Photoelectrochemical System

This study introduces an in situ fabrication of nanoporous hematite with a Ti‐doped SiO_x passivation layer for a high‐performance water‐splitting system. The nanoporous hematite with a Ti‐doped SiO_x layer (Ti‐(SiO_x/np‐Fe₂O₃)) has a photocurrent density of 2.44 mA cm^?2 at 1.23 V_RHE and 3.70 mA cm^?2 at 1.50 V_RHE. When a cobalt phosphate co‐catalyst was applied to Ti‐(SiO_x/np‐Fe₂O₃), the photocurrent density reached 3.19 mA cm^?2 at 1.23 V_RHE with stability, which shows great potential of the use of the Ti‐doped SiO_x layer with a synergistic effect of decreased charge recombination, the increased number of active sites, and the reduced hole‐diffusion pathway from the hematite to the electrolyte.     

Synthesis and Functional Reconstitution of Light‐Harvesting Complex II into Polymeric Membrane Architectures

One of most important processes in nature is the harvesting and dissipation of solar energy with the help of light‐harvesting complex II (LHCII). This protein, along with its associated pigments, is the main solar‐energy collector in higher plants. We aimed to generate stable, highly controllable, and sustainable polymer‐based membrane systems containing LHCII–pigment complexes ready for light harvesting. LHCII was produced by cell‐free protein synthesis based on wheat‐germ extract, and the successful integration of LHCII and its pigments into different membrane architectures was monitored. The unidirectionality of LHCII insertion was investigated by protease digestion assays. Fluorescence measurements indicated chlorophyll integration in the presence of LHCII in spherical as well as planar bilayer architectures. Surface plasmon enhanced fluorescence spectroscopy (SPFS) was used to reveal energy transfer from chlorophyll b to chlorophyll a, which indicates native folding of the LHCII proteins.     

Iron speciation related to color of Jurassic sedimentary rocks in Turpan Basin, northwest China

Mesozoic-Cenozoic reddish and green beds are widely distributed in northwest China. Mössbauer spectroscopy revealed that the composition of iron species varies with color in the middle-upper Jurassic sedimentary rocks from the Turpan Basin. Three main kinds of iron species were identified: (1) ferric iron of hematite (hem-Fe³⁺), (2) paramagnetic ferric iron (para-Fe³⁺), and (3) paramagnetic ferrous iron (para-Fe²⁺). Pyrite iron (pyr-Fe²⁺) was revealed only in a few samples. In general, there is a direct correlation between rock color, iron species and total iron content, however, in detail, this relationship is more complicated. The reddish rocks contain higher contents of total iron and hem-Fe³⁺, whereas the gray rocks contain much more para-Fe²⁺. However, relatively low hematite content cannot give red color to rocks, probably due to suppression by other pigments such as organic matter in black or chlorite in green. The dark or green rocks normally contain either only paramagnetic Fe²⁺ and paramagnetic Fe³⁺ species or these two species associated with hematite Fe³⁺, but the relative content of hematite species is lower. The variations of different iron species control lithological properties such as color and also may reflect the sedimentary conditions. Moreover, iron speciation in these rocks is one of the main factors, which result the color features of rocks in remote sensing imagery.This revised version was published online in November 2005 with corrections to the Cover Date.     

Identification of lead pigments in nanosamples from ancient paintings and polychromed sculptures using voltammetry of nanoparticles/atomic force microscopy

Voltammetry of nanoparticles coupled with atomic force microscopy was used to identify lead pigments in nanosamples proceeding from works of art. Upon mechanical attachment of few nanograms of sample to a graphite plate, well-defined voltammetric responses were obtained for lead orange, lead yellow, lead white, litharge, minium, Naples yellow, and tin-lead yellow, allowing for an unambiguous identification of such pigments. Atomic force images provide evidence for the occurrence of pigment-characteristic reduction processes accompanied by metal deposition on the graphite substrate. Electrochemical parameters are used for pigment identification. Application to the method for identifying lead pigments in different model binder + pigment specimens and pictorial samples from the canvas painting collection (anonymous, 17th century) of the Saint Joseph Church in Taormina (Italy), the frescoes painted by Antonio Acisclo Palomino y Velasco (1698) in the vault of the Sant Joan del Mercat church in València (Spain) and an anonymous polychromed sculpture (16th century) representing a Martyr Saint from Alacant (Spain) is described.     

Ultra‐Narrow Depletion Layers in a Hematite Mesocrystal‐Based Photoanode for Boosting Multihole Water Oxidation

Significant charge recombination that is difficult to suppress limits the practical applications of hematite (α‐Fe₂O₃) for photoelectrochemical water splitting. In this study, Ti‐modified hematite mesocrystal superstructures assembled from highly oriented tiny nanoparticle (NP) subunits with sizes of ca. 5 nm were developed to achieve the highest photocurrent density (4.3 mA cm^?2 at 1.23 V vs. RHE) ever reported for hematite‐based photoanodes under back illumination. Owing to rich interfacial oxygen vacancies yielding an exceedingly high carrier density of 4.1×10²¹ cm^?3 for super bulk conductivity in the electrode and a large proportion of ultra‐narrow depletion layers (<1 nm) inside the mesoporous film for significantly improved hole collection efficiency, a boosting of multihole water oxidation with very low activation energy (E_a=44 meV) was realized.     

Redshifted and Near‐infrared Active Analog Pigments Based upon Archaerhodopsin‐3

Archaerhodopsin‐3 (AR3) is a member of the microbial rhodopsin family of hepta‐helical transmembrane proteins, containing a covalently bound molecule of all‐trans retinal as a chromophore. It displays an absorbance band in the visible region of the solar spectrum (λmax 556 nm) and functions as a light‐driven proton pump in the archaeon Halorubrum sodomense. AR3 and its mutants are widely used in neuroscience as optogenetic neural silencers and in particular as fluorescent indicators of transmembrane potential. In this study, we investigated the effect of analogs of the native ligand all‐trans retinal A1 on the spectral properties and proton‐pumping activity of AR3 and its single mutant AR3 (F229S). While, surprisingly, the 3‐methoxyretinal A2 analog did not redshift the absorbance maximum of AR3, the analogs retinal A2 and 3‐methylamino‐16‐nor‐1,2,3,4‐didehydroretinal (MMAR) did generate active redshifted AR3 pigments. The MMAR analog pigments could even be activated by near‐infrared light. Furthermore, the MMAR pigments showed strongly enhanced fluorescence with an emission band in the near‐infrared peaking around 815 nm. We anticipate that the AR3 pigments generated in this study have widespread potential for near‐infrared exploitation as fluorescent voltage‐gated sensors in optogenetics and artificial leafs and as proton pumps in bioenergy‐based applications.     

A Series of Homo‐ and Heteroleptic Iron(III) Alkoxides as Precursors for Fe2O3

A series of bulky iron(III) alkoxides was synthesized by a ligand exchange reaction using [Fe(OtBu)₃]₂ and 2,4‐dimethylpentan‐3‐ol (HOdp). The resulting complexes are dimers, structural details are compared based on single crystal structure analyses. Investigation of the thermal properties shows a decrease of the melting point upon exchange of the tert‐butoxy by Odp^– ligands. Thermolysis leads to volatile products and the formation of phase pure hematite.     

Liquid-liquid solvent extraction of rare earths from chloride medium with sec-nonylphenoxy acetic acid and its mixtures with neutral organophosphorus extractants

In the present study, sec-nonylphenoxy acetic acid (CA100) and its mixtures with four neutral organophosphorus extractants, tri-butyl-phosphate (TBP), 2-ethylhexyl phosphonic acid di-2-ethyl ester (DEHEHP), Cyanex923, and Cyanex925 have been applied to the extraction of rare earths. Results show that all the four mixing systems do not have evident synergistic effects on the extraction of rare earths. The different extraction effects have been considered to the separation of rare earths. The four mixtures may be applied to the separation of yttrium from some certain lanthanoids at proper mole fractions of CA100.